US2360867A - Solvents for copolymers of butadiene hydrocarbons and alpha methylene nitriles - Google Patents

Description

- ard.

Patented Oct. 24, 1944 DIENE HYDROCARBONS vAND ALPHA METHYLENE Benjamin S. Garvey, Akron, Ohio, assignor to The B. F. Goodrich Company, New York, N. Y., a corporation of New York No Drawing.

6 Claims.

This invention relates to a new class of solvents for synthetic rubber of the type prepared by the copolymerization of a 'butadiene-1,3 hydrocarbon and an alpha methylene nitrile, and to the improved liquid compositions comprising Application October 2, Serial No. 413,303

such synthetic rubber dissolved in such new solvents.

It is well known that synthetic rubber of the type prepared by the copolymerization of a butadiene hydrocarbon and an alpha methylene nitrile is relatively much less soluble in common rubber solvents than is natural rubber or other Gasoline and other hydrocarsynthetic rubbers. bons, for examples, are excellent solvents for natvural rubber but absolutely fail to dissolve this type of synthetic rubber. Although some sol vents such as chlorinated hydrocarbons, esters and ketones to dissolve this type of synthetic rubber to a certain extent, they are not entirely satisfactory for use in the large scale production oi cements, coating compositions and the like.

Cements made by using esters and ketones as solvents generally gel quite easily and, accordingly, can not be extensively used. Ethylene dichloride is perhaps the best of the known solvents but it is quite toxic and its use. in large quantities constitutes a serious I have now discovered that saturated aliphatic hydrocarbon derivatives which contain at least one nitro group and which are liquid under ordinary conditions are excellent solvents for copolymers,

of butadlene hydrocarbons and alpha methylene nitriles. vent power for the copolymer; they yield cements which show no tendency to gel at ordinary temperatures even when the copolymer is used in fairly high concentrations; they are sufilciently volatile for most purposes and they are relatively non-toxic; Accordinglyv this invention comprises solutions 'of copolymers of butadiene hydrocarbons and alpha methylene nitriles in these new solvents. Such solutions may be used to make cements, paints, coating compounds and other liquid compositions for use in impregnating and coating articles of many diil'eren't kinds.

Among the saturated aliphatic hydrocarbon derivatives containing at least one nitro group, which are employed as solvents in this invention, there may be mentioned the liquid nitroparamns such as nitromethane, nitroethane, l-nitropropane, 2-nitro-propane, l-nitro-butane, 2-nitro-butane, l-nitro-pentane, 3-n'itroepentane, 1- nitro-hexane, 4-nitro-heptane, l-nitro-octane, 2-methyl-1-nitro-propr ne, I 2-methyl-3-nitro-bu- These materials possess a very high solinvention are employed to dissolve copolymers industrial hazam, l,l-dinitro -ethane, 1,1-dinitro-butane, 1,2--

dlnitro-butane, 2-methyl-2,3-dinitro-butane and the like; the liquid halogen substituted nitropar aflins such as l-chloro-l-nitro-propane', l-bromol-nitro-ethane, 1-iodo-2-nitro -butane, 2-nitro- 2,3-dichloro-butane and the like, the liquid hydroxy substituted nitro-paraillns such as 2-hydroxy-l-nitro propane, l-hydroxy 2 nitro-2- chloro-butane and the like and other liquid nitroparaffln derivatives containing other substituent groups such as alkoxy groups, acyl groups, cyano groups, nitroso groups, keto groups etc. The preferred solvents are liquids having the structure R-NO2 where R is a saturated aliphatic nucleus containing from 1 to 6 carbon atoms, since such compounds ordinarily possess the desired volatility.

Compounds of the above structure wherein R is an alkyl group or a halogen or hydroxyl substituted alkyl group containing from 1 to 6 carbon atoms are cheaper and more readily available and will usually be employed.

As mentioned hereinabove the solvents of this of butadiene-l,3 hydrocarbons and alpha methylene nitriles. Although copolymers of butadiene.'- l,3 and acrylonitrile are now commercially available and will ordinarily be used, other copolymers prepared from any 'of the butadiene+ 1,3 hydrocarbons including, in addition to butadiene-1,3, its homologs such as isoprene, 2,3-dimethyl butadiene-1,3, piperylene, etc., and .any

of the alpha methylene nitriles such as acrylonitrile, alpha-methyl acrylonitrlle, alpha-ethyl 'acrylonitrile, alpha-propyl acrylonitrile, alphachloroethyl acrylonitrile, 'etc., may also be employed. Substances prepared by the copolymerization 01! a mixture of several polymerizable' materials one of which is a butadiene-l,3 hydrc'carbon and another of which is an alpha methylene nitrile are also soluble in the solvents of this invention. Even though polymeric materials often vary in solubility depending upon the method used in preparing them, the solvents 2 assess? upon the use to be made of the compositions. In general the recipes and methods of mixing employedwill be analogous to those used in-preparing cements or coating compositions contain- T rubber mixed with other materials such as hat I ural rubber, softeners, pigments, fillers, antioxidents, accelerators, vulcanizing agents, etc. On the other hand the solvent may consist solely of a nitroparaflln or nitroparaflln derivative or a mixture of these or it may contain other sol-' vents such as'ethylene dichloride, benzene, toluene, chlorobenzene, Solvesso No. 1, a com-- mercially available aromatic type solvent, acetone, methyl ethyl ketone. ethyl acetate or the like mixed therewith. The proportion of the synthetic rubber or synthetic rubber compound dissolved in the solvent or solvent mixture may be as little -as-1% by weight, when very dilute solutions are required, or as high as 50% by weight or even higher when thick semi-liquid spreading compounds are the desired product.

To illustrate this invention a gram sample of a crude uncompounded synthetic rubber prepared b copolymerizing in aqueous emulsion '75 parts by weight of butadiene-1,3 and parts by weight of acrylonitrile is added'to 100 grams of nitroethane and the solvent is agitated until the synthetic rubber dissolves. Solution takes place in the same length of time required .when ethylene dichloride, an excellent solvent but a very toxic substance-is employed as the solvent. This solution may be kept indefinitely without gelling while similar solutions made using other solvents gel appreciably after a few hours time. When the solution is brushed on a surface the solvent evaporates rapidly leaving a clear film of the copolymer. 7

When the concentration of the synthetic rubber in the solvent isincreased to 20% by weight or higher, solutions which are somewhat more viscous but which still show no tendency to gel are obtained. Solutions ,of this concentration made using methyl ethyl ketone, benzene, chlorobenzene, Solvesso'No. 1," ethyl acetate and a number of other'common solvents gel so quickly that their use is very limited, but it has been found that by replacing a portion of such a solvent with one of the nitroparaflin solvents of this invention, solutions which do not gel are produced. For example, a cement made up by dissolving 20 grams of a copolymer, prepared by copolymerizing in aqueous emulsion 55 parts of butadiene and parts of acrylonitrile in a solvent mixtureconsisting of grams of l-chlorol-nitro-propane and 50 grams of chlorobenzene does not gel at; ordinary temperatures when kept for a long period of time.

As another example, a very concentrated cement is prepared by dissolving 2% lbs. of a composition containing 100 parts by weight of a :45 emulsion copolymer of butadiene and acrylonitrile, 50 parts by weight of channel'black and 50 parts by weight of a softener for the copolymer, in 1 gallon of a solvent mixture consisting of by volume of "Solvesso No. 1

, and only 25% by volume of nitro-ethane. Al-

though cements of this concentration prepared without using nitro-ethane in the solvent mixture gel quite rapidly, this cement shows no tendency to gel even after standing for oveir a month. i

In the above example the synthetic rubber is used in the compounded form rather than as the crude material. As another example of a solution containing such a compounded stock a synthetic rubber prepared by copolymerizing in aqueous emulsion 55 parts by weight of butadiene-1,3 and 45 parts by weight of acrylonitrile is compounded in the following recipe:

Parts by weight Butadiene-acrylonitrile copolymer 100.0 Channel black 50.0 Zinc oxide 5.0 Soft coal tar 25.0 Dibutyl phthalate 25.0 Phenyl-beta-naphthylamine 1.0 Stearic acid 1.0 Sulfur 2.0 Benzothiazyl disuliide 2.0

A gram sample of this compound is then dissolved in one quart of 1-nitro-butane. An excellent smooth cement which is useful in coating fabrics and in a number of other applications is obtained.

A solution containing vulcanizing agents like the one prepared above may 'be applied to a surface and heated to drive off the solvent and simultaneously vulcanize the copolymer or it may be allowed to dry without heating, vulcanization occurring slowly after the composition is applied to the surface. Compositions containing no sulfur or accelerator which do not vulcanize at all, as well as compositions designed to cure rapidly may also, of course, be prepared by appropriately selecting the various ingredients.

Adhesive compositions useful in adhering rubbery materials to each other or to porous or metallic surfaces may also be prepared by dissolving a butadiene acrylonitrile copolymer containing a sufficient amount of tackifying softeners in a nitro-paramn solvent. Such oil-resistant adhesive solutions are useful in many applications which, however, form no part of the present invention.

The specific examples are to be regarded as merely illustrative of the invention, and not in any sense restrictive. It will be obvious to those skilled in the art that many modifications such as substituting equivalent materials and varying the proportions of materials used are within the spirit and scope of the invention as defined in the app nded claims.

. I claim:

' atoms as a solvent for the said copolymer, the

said nitronaraflln being present in a concentration sufficient to dissolve all the said copolymer present to form a liquid free-flowing solution without benefit of the' action of'anjv other solvent. and the said cement being characterized by substantial freedom from the formation of ,re erslble gels .on prolonged standing.

2. A synthetic rubber cement comprising from 1 to 50% by weight of a copolymer of about 55 parts of butadiene-1;8 and 45 parts of acrylonitrile as the synthetic rubber constituent, and a liquid nitroparaffln of the formula R-NQ:

wherein R is an alkyl group containing from 1 to 6 carbon atoms as a solvent for the said copolymer, the said nitroparaflin being present in a concentration sumcient to dissolve all the said copclymer present to form a liquid free-flowing solution without benefit of the action of any v other solvent, and the said cement being characw terized by substantial freedom from the formation of reversible gels on prolonged standing.

3. A'synthetic rubber cement comprising .from 1 to 50% by weight of a copolymer-of butadiene- 1,3 with a lesser amount of acrylonitrile as the synthetic rubber constituent, and a nitrobutane as a solvent for the said copolymer-,.the nitro- Jmtane being'present in a concentration sumcient to dissolve all the said copolymer present benefit of the action of any other solvent, and the said cement being characterized by substantial freedom from the formation of reversible gels on prolonged standing. 7 4. A synthetic rubber cement comprising about 10% by weight of a copolymer of about 55 parts of butadiene-1,3 and about 45 parts of acrylonitrile, and a sufllcient amount of anitrobutane -to dissolve all the said copolymer to form a liquid formation of reversible gels on prolonged stand- 3 free flowing solution without benefit of the action of any other solvent, the said cement being characterized by substantial freedom from the in. v

5. A synthetic rubber cement comprising from 1 to 50% by'weight of a copolymer of about 55 parts of butadiene-l,3 and about 45 parts of 'to form a liquid free-flowing solution without acrylonitriledissolved in a solventi consisting solely of liquid nitroparafllns of the formula R-NO: wherein R is an alkyl group containing from 1 to 6 carbon atoms, .the said cement belng characterized by substantial freedom from the formation of reversible gels on prolonged standing.

6. A synthetic rubber cement comprising about 10% by weight of a copolymer of about'75. parts of butadiene-l,3 and about 25 parts of acrylonitrile and a sufficient amount of nitroethane to dissolve all the said copolymer to form a liquid free-flowing solution without benefit oi the action of any other solvent, the said cement being characterized by substantial freedom from the formation of reversible gels on prolonged stand- BENJAMIN B. GARVEY.